JP5241188B2 - Alkaline storage battery system - Google Patents

Alkaline storage battery system Download PDF

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JP5241188B2
JP5241188B2 JP2007253990A JP2007253990A JP5241188B2 JP 5241188 B2 JP5241188 B2 JP 5241188B2 JP 2007253990 A JP2007253990 A JP 2007253990A JP 2007253990 A JP2007253990 A JP 2007253990A JP 5241188 B2 JP5241188 B2 JP 5241188B2
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hydrogen storage
storage alloy
battery
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negative electrode
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JP2009087631A (en
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篤俊 赤穗
誠 越智
周平 吉田
和洋 北岡
正夫 武江
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Sanyo Electric Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H01M10/286—Cells or batteries with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/242—Hydrogen storage electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Description

本発明は、水素吸蔵合金を負極活物質とする水素吸蔵合金負極と水酸化ニッケルを主正極活物質とするニッケル正極とセパレータとからなる電極群をアルカリ電解液とともに外装缶内に備えたアルカリ蓄電池に係り、特に、ハイブリッド自動車（ＨＥＶ）、電気自動車（ＰＥＶ）などの車両用途に好適なアルカリ蓄電池システムに関する。   The present invention relates to an alkaline storage battery comprising an outer battery can with an electrode group comprising a hydrogen storage alloy negative electrode using a hydrogen storage alloy as a negative electrode active material, a nickel positive electrode using nickel hydroxide as a main positive electrode active material, and a separator together with an alkaline electrolyte. In particular, the present invention relates to an alkaline storage battery system suitable for use in a vehicle such as a hybrid vehicle (HEV) or an electric vehicle (PEV).

近年、二次電池の用途は、例えば、携帯電話、パーソナルコンピュータ、電動工具、電動自転車、ハイブリッド自動車（ＨＥＶ）、電気自動車（ＰＥＶ）など多岐に亘るようになった。これら用途のうち、特に、ハイブリッド自動車（ＨＥＶ）や電気自動車（ＰＥＶ）などのような車輌関係の用途においては、水素吸蔵合金負極を備えたアルカリ蓄電池が広く用いられている。そして、これらの車輌関係の用途に用いられるアルカリ蓄電池においては、高出力化の要望に加え、低コスト化の要望が高まっている。   2. Description of the Related Art In recent years, secondary batteries have been used in a wide variety of applications such as mobile phones, personal computers, electric tools, electric bicycles, hybrid vehicles (HEV), and electric vehicles (PEV). Among these applications, alkaline storage batteries including a hydrogen storage alloy negative electrode are widely used, particularly in vehicle-related applications such as hybrid vehicles (HEV) and electric vehicles (PEV). And in the alkaline storage battery used for these vehicle-related applications, in addition to the demand for higher output, the demand for cost reduction is increasing.

ところで、水素吸蔵合金負極を備えたアルカリ蓄電池の高出力化を達成するためには、希土類元素、マグネシウム、ニッケルを主要構成元素とする水素吸蔵合金の水素平衡圧を上げることが、特許文献１（特開２００５−３２５７３号公報）にて提案されるようになった。この特許文献１においては、水素吸蔵合金の水素平衡圧を上げることにより、水素濃度が上昇して放電性が向上（過電圧が低下）することが開示されている。また、水素吸蔵合金の水素平衡圧を上昇させることで電池の開路電圧が上昇し、放電性が向上することも開示されている。   By the way, in order to achieve high output of an alkaline storage battery equipped with a hydrogen storage alloy negative electrode, increasing the hydrogen equilibrium pressure of a hydrogen storage alloy containing rare earth elements, magnesium and nickel as main constituent elements is described in Patent Document 1 ( (Japanese Patent Laid-Open No. 2005-32573). In this Patent Document 1, it is disclosed that by increasing the hydrogen equilibrium pressure of the hydrogen storage alloy, the hydrogen concentration increases and the discharge performance improves (overvoltage decreases). It is also disclosed that the open circuit voltage of the battery is increased by increasing the hydrogen equilibrium pressure of the hydrogen storage alloy, and the discharge performance is improved.

一方、水素吸蔵合金負極を備えたアルカリ蓄電池において、水素吸蔵合金はコストの影響が最も大きい材料の１つであることが知られている。このため、このような高コストとなる水素吸蔵合金の使用量を削減すれば、この種のアルカリ蓄電池の低コスト化を達成することが可能となる。
特開２００５−３２５７３号公報 On the other hand, in an alkaline storage battery having a hydrogen storage alloy negative electrode, it is known that the hydrogen storage alloy is one of the materials having the greatest influence of cost. For this reason, if the usage-amount of the hydrogen storage alloy which becomes such a high cost is reduced, it will become possible to achieve the cost reduction of this kind of alkaline storage battery.
JP 2005-32573 A

しかしながら、上述した特許文献１にて提案されてるように、水素吸蔵合金の水素平衡圧を上昇させるために高水素平衡圧の水素吸蔵合金を用いると、この高水素平衡圧の水素吸蔵合金は耐久性に劣るということに起因して、この種の水素吸蔵合金負極を用いた電池の充放電サイクル特性（寿命）が低下するという問題を生じた。一方、低コスト化を達成するために水素吸蔵合金の使用量を削減すると、特に、低温度領域での出力低下を招来するという問題を生じた。   However, as proposed in Patent Document 1 described above, when a hydrogen storage alloy with a high hydrogen equilibrium pressure is used to increase the hydrogen equilibrium pressure of the hydrogen storage alloy, the hydrogen storage alloy with a high hydrogen equilibrium pressure is durable. Due to the inferiority of the battery, there arises a problem that the charge / discharge cycle characteristics (life) of the battery using this type of hydrogen storage alloy negative electrode is lowered. On the other hand, when the amount of the hydrogen storage alloy used is reduced in order to reduce the cost, there arises a problem that the output is lowered particularly in a low temperature region.

そこで、本発明は上記問題点を解消するためになされたものであって、Ａ成分に対するＢ成分のモル比となる化学量論比（Ｂ／Ａ）が高いＡ5Ｂ19型構造の結晶構造を有する水素吸蔵合金を用いて高出力、特に、低温度領域での高出力を確保するとともに水素吸蔵合金の使用量を大幅に削減することを可能にして低コスト化を達成する。また、部分充放電制御されるようにして充放電サイクル特性（寿命や耐久性）に優れたアルカリ蓄電システムを提供できるようにすることを目的とするものである。 Accordingly, the present invention has been made to solve the above problems, and has a crystal structure of an A 5 B 19 type structure having a high stoichiometric ratio (B / A) which is a molar ratio of the B component to the A component. By using the hydrogen storage alloy having the above, high output, in particular, high output in a low temperature region can be secured, and the amount of use of the hydrogen storage alloy can be greatly reduced to achieve cost reduction. It is another object of the present invention to provide an alkaline power storage system that is controlled in partial charge / discharge and is excellent in charge / discharge cycle characteristics (life and durability).

本発明のアルカリ蓄電池システムは、水素吸蔵合金を負極活物質とする水素吸蔵合金負極と水酸化ニッケルを主正極活物質とするニッケル正極とセパレータとからなる電極群をアルカリ電解液とともに外装缶内に備えたアルカリ蓄電池を有する。そして、上記目的を達成するため、水素吸蔵合金は、少なくともＡ5Ｂ19型構造の結晶構造を有し、かつ該Ａ5Ｂ19型構造のＡ成分に対するＢ成分のモル比となる化学量論比（Ｂ／Ａ）が３．８以上であるとともに、部分充放電制御するようになされており、前記部分充放電制御は、充電深度（ＳＯＣ）が１０％〜９５％相当の電圧範囲でのみ充放電されるように制御されていることを特徴とする。
The alkaline storage battery system of the present invention includes an electrode group comprising a hydrogen storage alloy negative electrode using a hydrogen storage alloy as a negative electrode active material, a nickel positive electrode using nickel hydroxide as a main positive electrode active material, and a separator in an outer can together with an alkaline electrolyte. It has an alkaline storage battery. In order to achieve the above object, the hydrogen storage alloy has a crystal structure of at least an A 5 B 19 type structure, and a stoichiometry that is a molar ratio of the B component to the A component of the A 5 B 19 type structure. The ratio (B / A) is 3.8 or more, and partial charge / discharge control is performed. The partial charge / discharge control is performed only in a voltage range corresponding to a charge depth (SOC) of 10% to 95%. It is controlled to be charged and discharged .

ここで、Ａ5Ｂ19型構造の結晶構造を有し、かつＡ5Ｂ19型構造のＡ成分に対するＢ成分のモル比となる化学量論比（Ｂ／Ａ）が３．８以上である水素吸蔵合金は、合金表面に増大したニッケル（Ｎｉ）リッチの反応活性点が存在する。このため、このような水素吸蔵合金を負極活物質として用いると、高出力を確保することが可能となる。また、合金表面に増大したニッケル（Ｎｉ）リッチの反応活性点が存在する水素吸蔵合金の使用量を削減しても、ニッケル（Ｎｉ）リッチの反応活性点が存在により高出力を維持することが可能となる。これにより、水素吸蔵合金の使用量を大幅に削減することが可能となって、低コスト化を達成できるようになる。 Here, has a crystal structure of the A 5 B 19 type structure, and the stoichiometric ratio of the molar ratio of B component to A component of A 5 B 19 type structure (B / A) is 3.8 or more The hydrogen storage alloy has an increased nickel (Ni) -rich reaction active site on the alloy surface. For this reason, when such a hydrogen storage alloy is used as a negative electrode active material, high output can be secured. In addition, even if the amount of hydrogen storage alloy in which nickel (Ni) -rich reaction active sites exist on the alloy surface is reduced, high output can be maintained due to the presence of nickel (Ni) -rich reaction active sites. It becomes possible. As a result, the amount of hydrogen storage alloy used can be greatly reduced, and cost reduction can be achieved.

また、Ａ5Ｂ19型構造の結晶構造を有し、かつＡ5Ｂ19型構造のＡ成分に対するＢ成分のモル比となる化学量論比（Ｂ／Ａ）が３．８以上である水素吸蔵合金を負極活物質とした水素吸蔵合金負極を備えたアルカリ蓄電池において、完全充放電サイクルを繰り返すように充放電制御を行うと、耐久性が低下するという実験結果が得られた。ところが、このようなアルカリ蓄電池を部分充放電制御がなされるようすると、耐久性が低下しないという実験結果が得られた。これは上述のような水素吸蔵合金を備えたアルカリ蓄電池に完全充放電サイクルを繰り返すと、水素吸蔵合金の微粉化が進行するためである。このようなことは、耐久性に優れたアルカリ蓄電システムとするためには部分充放電制御がなされるようにする必要があるということを意味している。 Moreover, A 5 B 19 type structure has a crystal structure, and the hydrogen stoichiometric ratio the molar ratio of B component to A component of A 5 B 19 type structure (B / A) is 3.8 or more In an alkaline storage battery having a hydrogen storage alloy negative electrode using a storage alloy as a negative electrode active material, when charge / discharge control was performed so as to repeat a complete charge / discharge cycle, an experimental result was obtained that durability was lowered. However, an experimental result was obtained that durability was not lowered when such an alkaline storage battery was subjected to partial charge / discharge control. This is because when the complete charge / discharge cycle is repeated on the alkaline storage battery including the hydrogen storage alloy as described above, the hydrogen storage alloy is pulverized. This means that partial charge / discharge control needs to be performed in order to obtain an alkaline power storage system with excellent durability.

なお、Ａ5Ｂ19型構造の結晶構造を有し、かつＡ5Ｂ19型構造のＡ成分に対するＢ成分のモル比となる化学量論比（Ｂ／Ａ）が３．８以上である水素吸蔵合金としては、一般式がＬｎl-xＭｇxＮｉy-a-bＡｌaＭb（式中、ＬｎはＹを含む希土類元素から選択される少なくとも１種の元素で、ＭはＣｏ，Ｍｎ，Ｚｎから選択される少なくとも１種の元素である）と表され、０．１≦ｘ≦０．２、３．８≦ｙ≦３．９、０．１≦ａ≦０．３、０≦ｂ≦０．２の条件を満たす必要がある。これは、ｘ＞０．２であるとマグネシウムの偏析が生じ、ａ＞０．３であるとアルミニウムの偏析が生じるようになって、それぞれ耐食性の低下をもたらすようになるからである。また、ｙ＜３．８であったり、ｙ＞３．９であったりすると、Ａ5Ｂ19型構造をそれぞれ構成することが困難となるからである。
Incidentally, A 5 B 19 type structure has a crystal structure, and molar ratio of hydrogen to become the stoichiometric ratio of B component to A component of A 5 B 19 type structure (B / A) is 3.8 or more As the storage alloy, the general formula is Ln lx Mg x Ni yab Al a M b (where Ln is at least one element selected from rare earth elements including Y, and M is selected from Co, Mn, Zn) At least one kind of element), 0.1 ≦ x ≦ 0.2. It is necessary to satisfy the conditions of 8 ≦ y ≦ 3.9, 0.1 ≦ a ≦ 0.3, and 0 ≦ b ≦ 0.2. This is because magnesium is segregated when x> 0.2, and aluminum is segregated when a> 0.3, resulting in a decrease in corrosion resistance. In addition, y <3. If it is 8 or y> 3.9, it is difficult to construct the A 5 B 19 type structure.

ここで、ニッケル正極の容量Ｘに対する水素吸蔵合金負極の容量Ｙの比率となる容量比Ｚ（＝Ｙ／Ｘ）が１．２以下（１．０＜Ｚ≦１．２）なるように水素吸蔵合金の使用量を削減した水素吸蔵合金負極を備えたアルカリ蓄電池においては、部分充放電制御がなされるようすると、耐久性が低下しないという実験結果が得られた。このため、水素吸蔵合金の使用量を大幅に削減することを可能にして低コスト化を達成するためには、ニッケル正極の容量Ｘに対する水素吸蔵合金負極の容量Ｙの比率となる容量比Ｚ（＝Ｙ／Ｘ）が１．２以下（１．０＜Ｚ≦１．２）なるように水素吸蔵合金の使用量を削減するのが好ましい。   Here, hydrogen storage is performed so that the capacity ratio Z (= Y / X), which is the ratio of the capacity Y of the hydrogen storage alloy negative electrode to the capacity X of the nickel positive electrode, is 1.2 or less (1.0 <Z ≦ 1.2). In the alkaline storage battery provided with the hydrogen storage alloy negative electrode in which the amount of the alloy used was reduced, an experimental result was obtained that durability was not lowered when partial charge / discharge control was performed. For this reason, in order to achieve a reduction in cost by making it possible to significantly reduce the amount of hydrogen storage alloy used, a capacity ratio Z (the ratio of the capacity Y of the hydrogen storage alloy negative electrode to the capacity X of the nickel positive electrode) = Y / X) It is preferable to reduce the amount of hydrogen storage alloy used so that 1.2 or less (1.0 <Z ≦ 1.2).

ところが、ニッケル正極の容量Ｘに対する水素吸蔵合金負極の容量Ｙの比率となる容量比Ｚ（＝Ｙ／Ｘ）が１．２以下（１．０＜Ｚ≦１．２）なるように水素吸蔵合金の使用量を削減した水素吸蔵合金負極を備えたアルカリ蓄電池においては、完全充放電サイクルを繰り返すような完全充放電制御を行うようにすると、耐久性が低下するという実験結果が得られた。その理由は、水素吸蔵合金の使用量を削減したことにより、負極での酸素ガス吸収量が減少し、これに伴って電池内圧が上昇するようになって、負極活物質が芯体から剥離する現象が起こりやすくなり、完全充放電サイクルの進行に伴って出力が低下し、耐久性が低下したと考えられるからである。   However, the hydrogen storage alloy is such that the capacity ratio Z (= Y / X), which is the ratio of the capacity Y of the hydrogen storage alloy negative electrode to the capacity X of the nickel positive electrode, is 1.2 or less (1.0 <Z ≦ 1.2). In the alkaline storage battery provided with the hydrogen storage alloy negative electrode in which the amount of use was reduced, an experimental result was obtained that durability was lowered when complete charge / discharge control was performed such that the complete charge / discharge cycle was repeated. The reason is that by reducing the amount of hydrogen storage alloy used, the amount of oxygen gas absorbed by the negative electrode decreases, and the internal pressure of the battery increases accordingly, and the negative electrode active material peels from the core. This is because the phenomenon is likely to occur, the output decreases as the complete charge / discharge cycle progresses, and the durability is considered to have decreased.

この場合、部分充放電制御は、複数の電池を組み合わせた組電池とした場合に各電池間にバラツキが生じない電圧（この場合は、充電深度（ＳＯＣ）が１０％相当の電圧）に達すると放電を停止して充電を開始し、酸素過電圧に到達する前の電圧（この場合は、充電深度（ＳＯＣ）が９５％相当の電圧）に達すると充電を停止して放電を開始するようになされるようにすればよい。なお、実用的には、充電深度（ＳＯＣ）が２０％相当の電圧に達すると放電を停止して充電を開始し、充電深度（ＳＯＣ）が８０％相当の電圧に達すると充電を停止して放電を開始するように部分充放電制御がなされるのが好ましい。   In this case, when the partial charge / discharge control reaches a voltage (in this case, a voltage corresponding to 10% charge depth (SOC)) in which there is no variation between the batteries when the assembled battery is a combination of a plurality of batteries. The charging is stopped and the charging is started. When the voltage before reaching the oxygen overvoltage (in this case, the charging depth (SOC) is equivalent to 95%) is reached, the charging is stopped and the discharging is started. You can do so. Practically, when the depth of charge (SOC) reaches a voltage equivalent to 20%, the discharge is stopped and charging is started, and when the depth of charge (SOC) reaches a voltage equivalent to 80%, the charge is stopped. It is preferable that partial charge / discharge control is performed so as to start discharge.

本発明においては、Ａ成分に対するＢ成分のモル比となる化学量論比（Ｂ／Ａ）が高いＡ5Ｂ19型構造の結晶構造を有する水素吸蔵合金を用いているので、高出力、特に、低温度領域での高出力を確保することが可能になるとともに水素吸蔵合金の使用量を大幅に削減することを可能にして低コスト化を達成することが可能となる。また、部分充放電制御されるようにして耐久性に優れたアルカリ蓄電システムを提供できるようになる。 In the present invention, since a hydrogen storage alloy having a crystal structure of A 5 B 19 type structure having a high stoichiometric ratio (B / A) as a molar ratio of the B component to the A component is used, a high output, particularly In addition, it becomes possible to secure a high output in a low temperature region, and to significantly reduce the amount of hydrogen storage alloy used, thereby achieving a reduction in cost. In addition, it is possible to provide an alkaline power storage system with excellent durability by performing partial charge / discharge control.

本発明の実施の形態を以下に説明するが、本発明はこれに限定されるものでなく、その要旨を変更しない範囲で適宜変更して実施することができる。なお、図１は本発明のアルカリ蓄電池システムに用いられるアルカリ蓄電池を模式的に示す断面図である。   Embodiments of the present invention will be described below. However, the present invention is not limited to these embodiments, and can be appropriately modified and implemented without departing from the scope of the present invention. In addition, FIG. 1 is sectional drawing which shows typically the alkaline storage battery used for the alkaline storage battery system of this invention.

１．水素吸蔵合金負極
本発明の水素吸蔵合金負極１１はパンチングメタルからなる負極芯体に水素吸蔵合金スラリーが充填されて形成されている。この場合、まず、一般式がＬｎl-xＭｇxＮｉy-a-bＡｌaＭb（式中、ＬｎはＹを含む希土類元素から選択される少なくとも１種の元素で、ＭはＣｏ，Ｍｎ，Ｚｎから選択される少なくとも１種の元素であり、０．１≦ｘ≦０．２、３．８≦ｙ≦３．９、０．１≦ａ≦０．３、０≦ｂ≦０．２）で表されるようにＮｄ，Ｍｇ，Ｎｉ，Ａｌ，Ｃｏなどの金属元素を所定のモル比となるように混合する。ついで、これらの混合物をアルゴンガス雰囲気の高周波誘導炉に投入して溶解させた後、合金鋳塊になるように溶湯急冷して、水素吸蔵合金を得る。
1. Hydrogen Storage Alloy Negative Electrode The hydrogen storage alloy negative electrode 11 of the present invention is formed by filling a negative electrode core made of punching metal with a hydrogen storage alloy slurry. In this case, first, the general formula is Ln lx Mg x Ni yab Al a M b (where Ln is at least one element selected from rare earth elements including Y, and M is selected from Co, Mn, and Zn). at least one element that is represented by 0.1 ≦ x ≦ 0.2,3. 8 ≦ y ≦ 3.9,0.1 ≦ a ≦ 0.3,0 ≦ b ≦ 0.2) As described above, metal elements such as Nd, Mg, Ni, Al, and Co are mixed so as to have a predetermined molar ratio. Next, these mixtures are put into a high-frequency induction furnace in an argon gas atmosphere and melted, and then the molten metal is rapidly cooled to form an alloy ingot to obtain a hydrogen storage alloy.

ついで、得られた水素吸蔵合金について、ＤＳＣ（示差走査熱量計）を用いて融点（Ｔ
ｍ）を測定する。その後、水素吸蔵合金の融点（Ｔｍ）よりも３０℃だけ低い温度（Ｔａ＝Ｔｍ−３０℃）で所定時間（この場合は１０時間）の熱処理を行って、得られた水素吸蔵合金がＡ5Ｂ19型構造となるように調整し、これらを水素吸蔵合金α，β，γとした。
ここで、熱処理後の各水素吸蔵合金α〜γの組成を高周波プラズマ分光法（ＩＣＰ）によって分析したところ、水素吸蔵合金αは組成式がＮｄ0.9Ｍｇ0.1Ｎｉ3.2Ａｌ0.2Ｃｏ0.1（希土類を含むＡ成分が１．０モルで、Ｎｉを含むＢ成分が３．５モルで、それらの化学量論比Ｂ／Ａが３．５となる）で表されることが分かった。
Next, the obtained hydrogen storage alloy was measured for the melting point (T) using a DSC (differential scanning calorimeter).
m) is measured. Thereafter, a heat treatment is performed at a temperature lower than the melting point (Tm) of the hydrogen storage alloy by 30 ° C. (Ta = Tm−30 ° C.) for a predetermined time (in this case, 10 hours), and the obtained hydrogen storage alloy is A 5. It adjusted so that it might become a B19 type structure, and let these be hydrogen storage alloy alpha, beta, and gamma.
Here, when the composition of each of the hydrogen storage alloys α to γ after the heat treatment was analyzed by high frequency plasma spectroscopy (ICP), the composition formula of the hydrogen storage alloy α was Nd 0.9 Mg 0.1 Ni 3.2 Al 0.2 Co 0.1 ( including rare earths) . It was found that the A component was 1.0 mol, the B component containing Ni was 3.5 mol, and the stoichiometric ratio B / A was 3.5.

また、水素吸蔵合金βは組成式がＬａ0.2Ｐｒ0.1Ｎｄ0.5Ｍｇ0.2Ｎｉ3.5Ａｌ0.3（希土類を含むＡ成分が１．０モルで、Ｎｉを含むＢ成分が３．８モルで、それらの化学量論比Ｂ／Ａが３．８となる）で表されることが分かった。さらに、水素吸蔵合金γはＬａ0.5Ｐｒ0.1Ｎｄ0.3Ｍｇ0.1Ｎｉ3.7Ａｌ0.2（希土類を含むＡ成分が１．０モルで、Ｎｉを含むＢ成分が３．９モルで、それらの化学量論比Ｂ／Ａが３．９となる）で表されることが分かった。
Further, the hydrogen storage alloy β has a composition formula of La 0.2 Pr 0.1 Nd 0.5 Mg 0.2 Ni 3.5 Al 0.3 (1.0 mol of the A component containing rare earth and 3.8 mol of the B component containing Ni, and their chemistry) The stoichiometric ratio B / A is 3.8). Further, the hydrogen storage alloy γ is La 0.5 Pr 0.1 Nd 0.3 Mg 0.1 Ni 3.7 Al 0.2 (A component containing rare earth is 1.0 mol, B component containing Ni is 3.9 mol, and their stoichiometric ratio is B / A is 3.9).

なお、Ｃｕ−Ｋα管をＸ線源とするＸ線回折測定装置を用いる粉末Ｘ線回折法で各水素吸蔵合金α〜γの結晶構造の同定を以下のようにして行った。この場合、スキャンスピード１°／ｍｉｎ、管電圧４０ｋＶ、管電流３００ｍＡ、スキャンステップ１°、測定角度（２θ）２０〜５０°でＸ線回折測定を行う。そして、得られたＸＲＤプロファイルよりＪＣＰＤＳカードチャートを用いて、各水素吸蔵合金α〜γの結晶構造を同定すると、Ａ5Ｂ19型構造（Ｃｅ5Ｃｏ19型構造）であることが確認できた。 The crystal structures of the hydrogen storage alloys α to γ were identified as follows by powder X-ray diffractometry using an X-ray diffractometer using a Cu—Kα tube as an X-ray source. In this case, X-ray diffraction measurement is performed at a scan speed of 1 ° / min, a tube voltage of 40 kV, a tube current of 300 mA, a scan step of 1 °, and a measurement angle (2θ) of 20 to 50 °. Then, by using the JCPDS card chart from XRD profiles thus obtained, when identifying the crystal structure of the hydrogen storage alloy Arufa～ganma, it was confirmed that the A 5 B 19 type structure (Ce 5 Co 19 type structure) .

ついで、得られた各水素吸蔵合金α〜γを不活性雰囲気中で機械的に粉砕し、篩分けにより４００メッシュ〜２００メッシュの間に残る合金粉末を選別する。なお、レーザ回折・散乱式粒度分布測定装置により粒度分布を測定すると、質量積分５０％にあたる平均粒径は２５μｍであった。この後、得られた水素吸蔵合金粉末１００質量部に対し、非水溶性高分子結着剤としてのＳＢＲ（スチレンブタジエンラテックス）を０．５質量部と、増粘剤としてＣＭＣ（カルボキシメチルセルロース）を０．０３質量部と、適量の純水を加えて混練して、水素吸蔵合金スラリーａ，ｂ，ｃを調製する。   Next, the obtained hydrogen storage alloys α to γ are mechanically pulverized in an inert atmosphere, and the alloy powder remaining between 400 mesh and 200 mesh is selected by sieving. When the particle size distribution was measured with a laser diffraction / scattering type particle size distribution measuring device, the average particle size corresponding to 50% of the mass integral was 25 μm. Thereafter, 0.5 parts by mass of SBR (styrene butadiene latex) as a water-insoluble polymer binder and CMC (carboxymethylcellulose) as a thickener are added to 100 parts by mass of the obtained hydrogen storage alloy powder. 0.03 parts by mass and an appropriate amount of pure water are added and kneaded to prepare hydrogen storage alloy slurries a, b, and c.

ここで、水素吸蔵合金αからなるものを水素吸蔵合金スラリーａとし、水素吸蔵合金βからなるものを水素吸蔵合金スラリーｂとし、水素吸蔵合金γからなるものを水素吸蔵合金スラリーｃとする。
そして、得られた水素吸蔵合金スラリーａ，ｂ，ｃをパンチングメタル（ニッケルメッキ鋼板製）からなる負極芯体の両面に塗着した後、室温で乾燥させ、所定の充填密度になるように圧延した後、所定の寸法（例えば、８０ｃｍ×５ｃｍ）に裁断することにより水素吸蔵合金負極１１（ａ１，ｂ１，ｃ１およびａ２，ｂ２，ｃ２）が作製される。 Here, a hydrogen storage alloy slurry a is made of hydrogen storage alloy α, a hydrogen storage alloy slurry b is made of hydrogen storage alloy β, and a hydrogen storage alloy slurry c is made of hydrogen storage alloy γ.
And after apply | coating the obtained hydrogen storage alloy slurry a, b, c to both surfaces of the negative electrode core body which consists of punching metals (made by nickel plating steel plate), it is made to dry at room temperature and rolled so that it may become a predetermined filling density. After that, the hydrogen storage alloy negative electrode 11 (a1, b1, c1 and a2, b2, c2) is manufactured by cutting into a predetermined dimension (for example, 80 cm × 5 cm).

ここで、水素吸蔵合金スラリーａを用い、後述するニッケル正極１２の正極容量に対する容量比が１．２となるように負極容量が調整されたものを水素吸蔵合金負極ａ１とした。同様に、水素吸蔵合金スラリーｂを用い、ニッケル正極１２の正極容量に対する容量比が１．２となるように負極容量が調整されたものを水素吸蔵合金負極ｂ１とし、水素吸蔵合金スラリーｃを用い、ニッケル正極１２の正極容量に対する容量比が１．２となるように負極容量が調整されたものを水素吸蔵合金負極ｃ１とした。   Here, the hydrogen storage alloy negative electrode a1 was prepared by using the hydrogen storage alloy slurry a and adjusting the negative electrode capacity so that the capacity ratio with respect to the positive electrode capacity of the nickel positive electrode 12 described later becomes 1.2. Similarly, the hydrogen storage alloy slurry b is used, and the negative electrode capacity adjusted so that the capacity ratio of the nickel positive electrode 12 to the positive electrode capacity is 1.2 is referred to as a hydrogen storage alloy negative electrode b1, and the hydrogen storage alloy slurry c is used. The negative electrode capacity was adjusted so that the capacity ratio of the nickel positive electrode 12 to the positive electrode capacity was 1.2 was designated as a hydrogen storage alloy negative electrode c1.

また、水素吸蔵合金スラリーａを用い、ニッケル正極１２の正極容量に対する容量比が１．７となるように負極容量が調整されたものを水素吸蔵合金負極ａ２とし、水素吸蔵合金スラリーｂを用い、ニッケル正極１２の正極容量に対する容量比が１．７となるように負極容量が調整されたものを水素吸蔵合金負極ｂ２とし、水素吸蔵合金スラリーｃを用い、ニッケル正極１２の正極容量に対する容量比が１．７となるように負極容量が調整されたものを水素吸蔵合金負極ｃ２とした。   Further, the hydrogen storage alloy slurry a was used, and the negative electrode capacity adjusted so that the capacity ratio to the positive electrode capacity of the nickel positive electrode 12 was 1.7 was referred to as a hydrogen storage alloy negative electrode a2, and the hydrogen storage alloy slurry b was used. The negative electrode capacity adjusted so that the capacity ratio of the nickel positive electrode 12 to the positive electrode capacity is 1.7 is referred to as a hydrogen storage alloy negative electrode b2, and the hydrogen storage alloy slurry c is used. What adjusted the negative electrode capacity | capacitance so that it might be set to 1.7 was made into the hydrogen storage alloy negative electrode c2.

３．ニッケル正極
一方、ニッケル正極１２は、基板となるニッケル焼結基板の多孔内に所定量の水酸化ニッケルと水酸化コバルトと水酸化亜鉛とが充填されて形成されている。
この場合、ニッケル焼結基板は、まず、例えば、ニッケル粉末に、増粘剤となるメチルセルロース（ＭＣ）と高分子中空微小球体（例えば、孔径が６０μｍのもの）と水とを混合、混練してニッケルスラリーが作製されている。ついで、ニッケルめっき鋼板からなるパンチングメタルの両面にニッケルスラリーを塗着した後、還元性雰囲気中で１０００℃で加熱して、塗着されている増粘剤や高分子中空微小球体を消失させるとともにニッケル粉末同士を焼結することにより作製されている。 3. Nickel Positive Electrode On the other hand, the nickel positive electrode 12 is formed by filling a predetermined amount of nickel hydroxide, cobalt hydroxide, and zinc hydroxide in the pores of a nickel sintered substrate serving as a substrate.
In this case, the nickel sintered substrate is first prepared by mixing and kneading, for example, nickel powder with methyl cellulose (MC) as a thickener, polymer hollow microspheres (for example, having a pore diameter of 60 μm), and water. A nickel slurry has been made. Next, after applying nickel slurry on both sides of the punching metal made of nickel-plated steel plate, it is heated at 1000 ° C. in a reducing atmosphere, and the applied thickener and polymer hollow microspheres disappear. It is produced by sintering nickel powders.

そして、得られたニッケル焼結基板に以下のような含浸液を含浸した後、アルカリ処理液によるアルカリ処理を所定回数繰り返すことにより、ニッケル焼結基板の多孔内に所定量の水酸化ニッケルと水酸化亜鉛とが充填される。この後、所定の寸法（例えば、２．５ｃｍ×２．５ｃｍ）に裁断することにより、正極活物質が充填されたニッケル正極１２が作製される。この場合、含浸液としては、硝酸ニッケルと硝酸コバルトと硝酸亜鉛のモル比が１００：５：５となる比重が１．８の混合水溶液を用い、アルカリ処理液としては、比重が１．３の水酸化ナトリウム（ＮａＯＨ）水溶液を用いるようにしている。   Then, after impregnating the obtained nickel sintered substrate with the following impregnating liquid, the alkali treatment with the alkali treatment liquid is repeated a predetermined number of times, whereby a predetermined amount of nickel hydroxide and water are placed in the pores of the nickel sintered substrate. Filled with zinc oxide. Thereafter, the nickel positive electrode 12 filled with the positive electrode active material is manufactured by cutting into a predetermined dimension (for example, 2.5 cm × 2.5 cm). In this case, as the impregnating liquid, a mixed aqueous solution having a specific gravity of 1.8 in which the molar ratio of nickel nitrate, cobalt nitrate, and zinc nitrate is 100: 5: 5 is used, and the specific gravity is 1.3 as the alkali treatment liquid. A sodium hydroxide (NaOH) aqueous solution is used.

そして、ニッケル焼結基板を含浸液に浸漬して、ニッケル焼結基板の細孔内に含浸液を含浸させた後、乾燥させ、ついで、アルカリ処理液に浸漬してアルカリ処理を行う。これにより、ニッケル塩や亜鉛塩を水酸化ニッケルや水酸化亜鉛に転換させる。この後、充分に水洗してアルカリ溶液を除去した後、乾燥させる。このような、含浸液の含浸、乾燥、アルカリ処理液への浸漬、水洗、および乾燥という一連の正極活物質の充填操作を６回繰り返すことにより、所定量の正極活物質がニッケル焼結基板に充填される。   Then, the nickel sintered substrate is immersed in the impregnating solution, the impregnating solution is impregnated in the pores of the nickel sintered substrate, dried, and then immersed in the alkali processing solution to perform the alkali treatment. Thereby, nickel salt and zinc salt are converted into nickel hydroxide and zinc hydroxide. Thereafter, it is sufficiently washed with water to remove the alkaline solution and then dried. A series of positive electrode active material filling operations such as impregnation with an impregnation solution, drying, immersion in an alkali treatment solution, washing with water, and drying are repeated six times, whereby a predetermined amount of the positive electrode active material is applied to the nickel sintered substrate. Filled.

４．ニッケル−水素蓄電池
ついで、上述のようにして作製される水素吸蔵合金負極１１（ａ１，ｂ１，ｃ１およびａ２，ｂ２，ｃ２）と、ニッケル正極１２とを用い、これらの間に、目付が５５ｇ／ｃｍ2のポリオレフィン製不織布からなるセパレータ１３を介在させて渦巻状に巻回することにより渦巻状電極群が作製される。なお、このようにして作製される渦巻状電極群の下部には水素吸蔵合金負極１１の芯体露出部１１ｃが露出しており、その上部にはニッケル正極１２の芯体露出部１２ｃが露出している。ついで、得られた渦巻状電極群の下端面に露出する芯体露出部１１ｃに負極集電体１４を溶接するとともに、渦巻状電極群の上端面に露出するニッケル正極１２の芯体露出部１２ｃの上に正極集電体１５を溶接して、電極体が作製される。 4). Nickel-hydrogen storage battery Next, the hydrogen storage alloy negative electrode 11 (a1, b1, c1 and a2, b2, c2) produced as described above and the nickel positive electrode 12 were used, and the basis weight was 55 g / A spiral electrode group is produced by winding a separator 13 made of a polyolefin nonwoven fabric of cm 2 in a spiral shape. The core exposed portion 11c of the hydrogen storage alloy negative electrode 11 is exposed at the lower part of the spiral electrode group thus manufactured, and the core exposed part 12c of the nickel positive electrode 12 is exposed at the upper portion thereof. ing. Next, the negative electrode current collector 14 is welded to the core exposed portion 11c exposed at the lower end surface of the obtained spiral electrode group, and the core exposed portion 12c of the nickel positive electrode 12 exposed at the upper end surface of the spiral electrode group. A positive electrode current collector 15 is welded onto the electrode body to produce an electrode body.

ついで、得られた電極体を鉄にニッケルメッキを施した有底筒状の外装缶（底面の外面は負極外部端子となる）１７内に収納した後、負極集電体１４を外装缶１７の内底面に溶接する。一方、正極集電体１５より延出する集電リード部１５ａを正極端子を兼ねるとともに外周部に絶縁ガスケット１９が装着された封口体１８の底部に溶接する。なお、封口体１８には正極キャップ１８ａが設けられていて、この正極キャップ１８ａ内に所定の圧力になると変形する弁体１８ｂとスプリング１８ｃよりなる圧力弁（図示せず）が配置されている。   Next, after the obtained electrode body was accommodated in a bottomed cylindrical outer can in which nickel was plated on iron (the outer surface of the bottom surface becomes a negative external terminal) 17, the negative electrode current collector 14 was attached to the outer can 17. Weld to the inner bottom. On the other hand, the current collecting lead portion 15a extending from the positive electrode current collector 15 serves as a positive electrode terminal and is welded to the bottom portion of the sealing body 18 having the insulating gasket 19 attached to the outer peripheral portion. The sealing body 18 is provided with a positive electrode cap 18a, and a pressure valve (not shown) composed of a valve body 18b and a spring 18c, which are deformed when a predetermined pressure is reached, is disposed in the positive electrode cap 18a.

ついで、外装缶１７の上部外周部に環状溝部１７ａを形成した後、電解液を注液し、外装缶１７の上部に形成された環状溝部１７ａの上に封口体１８の外周部に装着された絶縁ガスケット１９を載置する。この後、外装缶１７の開口端縁１７ｂをかしめることにより、電池容量は６ＡｈでＤサイズ（直径が３２ｍｍで、高さが６０ｍｍ）のニッケル−水素蓄電池１０（Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２）が作製される。この場合、外装缶１７内にアルカリ電解液（水酸化ナトリウム（ＮａＯＨ）と水酸化カリウム（ＫＯＨ）と水酸化リチウム（ＬｉＯＨ）との混合水溶液）が電池容量（Ａｈ）当り２．５ｇ（２．５ｇ／Ａｈ）となるように注入されている。   Next, after forming an annular groove portion 17 a on the upper outer peripheral portion of the outer can 17, an electrolytic solution was injected, and the outer peripheral portion of the sealing body 18 was mounted on the annular groove portion 17 a formed on the upper portion of the outer can 17. An insulating gasket 19 is placed. Thereafter, by crimping the opening edge 17b of the outer can 17, the battery capacity is 6Ah and the D-size (diameter is 32mm, height is 60mm) nickel-hydrogen storage battery 10 (A1, B1, C1, A2, B2, C2) are produced. In this case, an alkaline electrolyte (mixed aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (KOH), and lithium hydroxide (LiOH)) in the outer can 17 is 2.5 g per battery capacity (Ah) (2. 5 g / Ah).

ここで、水素吸蔵合金負極ａ１（化学量論比が３．５の合金を用い容量比が１．２のもの）を用いたものを電池Ａ１とし、水素吸蔵合金負極ｂ１（化学量論比が３．８の合金を用い容量比が１．２のもの）を用いたものを電池Ｂ１とし、水素吸蔵合金負極ｃ１（化学量論比が３．９の合金を用い容量比が１．２のもの）を用いたものを電池Ｃ１とした。また、水素吸蔵合金負極ａ２（化学量論比が３．５の合金を用い容量比が１．７のもの）を用いたものを電池Ａ２とし、水素吸蔵合金負極ｂ２（化学量論比が３．８の合金を用い容量比が１．７のもの）を用いたものを電池Ｂ２とし、水素吸蔵合金負極ｃ２（化学量論比が３．９の合金を用い容量比が１．７のもの）を用いたものを電池Ｃ２とした。   Here, a battery using the hydrogen storage alloy negative electrode a1 (an alloy having a stoichiometric ratio of 3.5 and a capacity ratio of 1.2) is referred to as a battery A1, and a hydrogen storage alloy negative electrode b1 (a stoichiometric ratio of A battery B1 using an alloy of 3.8 and a capacity ratio of 1.2) is referred to as a battery B1, and a hydrogen storage alloy negative electrode c1 (an alloy having a stoichiometric ratio of 3.9 and a capacity ratio of 1.2). A battery C1 was used. A battery using the hydrogen storage alloy negative electrode a2 (an alloy having a stoichiometric ratio of 3.5 and a capacity ratio of 1.7) is referred to as a battery A2, and a hydrogen storage alloy negative electrode b2 (a stoichiometric ratio of 3). Battery B2 is used with an alloy of .8 with a capacity ratio of 1.7) and a hydrogen storage alloy negative electrode c2 (with an alloy with a stoichiometric ratio of 3.9 and a capacity ratio of 1.7). ) Was designated as Battery C2.

４．電池試験
（１）低温出力試験
ついで、各電池Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２について、電池容量に対して１Ｉｔの充電電流で電池容量の５０％まで充電（ＳＯＣ（State Of Charge：充電深度）が５０％となるように３０分の充電）した。この後、電池表面温度が−１０℃になるまで冷却した後、１Ｉｔ充電→２Ｉｔ放電→２Ｉｔ充電→４Ｉｔ放電→３Ｉｔ充電→６Ｉｔ放電→４Ｉｔ充電→８Ｉｔ放電→５Ｉｔ充電→１０Ｉｔ放電の順で充放電を繰り返した。 4). Battery Test (1) Low Temperature Output Test Next, each battery A1, B1, C1, A2, B2, C2 is charged to 50% of the battery capacity with a charge current of 1 It to the battery capacity (SOC (State Of Charge) The battery was charged for 30 minutes so that the depth) was 50%. Then, after cooling until the battery surface temperature reaches −10 ° C., charging is performed in the order of 1 It charge → 2 It discharge → 2 It charge → 4 It discharge → 3 It charge → 6 It discharge → 4 It charge → 8 It discharge → 5 It charge → 10 It discharge. The discharge was repeated.

この際、各ステップの間に１０分間の休止期問を設け、各放電ステップ実施後の１０分間の休止後において、１０秒間ずつ放電、２０秒間ずつ充電を行い、この１０秒間経過時点における電池電圧を放電電流に対してプロットし、最小二乗法にて求めた直線が０．９Ｖに達するときの電流値を−１０℃出力として求めた。そして、電池Ａ２の−１０℃出力を１００としたときの各電池Ａ１，Ｂ１，Ｃ１，Ｂ２，Ｃ２の比率（相対値）を−１０℃出力比として求めると下記の表１に示すような結果となった。

Figure 0005241188
At this time, a 10-minute rest period is provided between each step, and after 10-minute rest after each discharge step, the battery is discharged every 10 seconds and charged every 20 seconds. Was plotted against the discharge current, and the current value when the straight line obtained by the least square method reached 0.9 V was obtained as the -10 ° C output. Then, when the ratio (relative value) of each battery A1, B1, C1, B2, and C2 when the -10 ° C output of the battery A2 is set to 100 is obtained as the -10 ° C output ratio, the results shown in Table 1 below are obtained. It became.
Figure 0005241188

上記表１の結果から、以下のことが明らかになった。即ち、ニッケル正極の容量との容量比が１．７で合金の化学量論比が３．５の水素吸蔵合金負極ａ２を用いた電池Ａ２においては、現状のＨＥＶ用途においては充分な高出力が得られないニッケル−水素蓄電池であることが分かった。これは化学量論比が３．５の水素吸蔵合金においてはＮｉリッチな反応活性点が少ないためと考えられる。   From the results in Table 1 above, the following became clear. That is, in the battery A2 using the hydrogen storage alloy negative electrode a2 having a capacity ratio of 1.7 with respect to the capacity of the nickel positive electrode and an alloy stoichiometric ratio of 3.5, a sufficiently high output is obtained in the current HEV application. It was found that the nickel-hydrogen storage battery was not obtained. This is probably because the hydrogen storage alloy having a stoichiometric ratio of 3.5 has few Ni-rich reaction active sites.

また、ニッケル正極の容量との容量比が１．７で合金の化学量論比が３．８の水素吸蔵合金負極ｂ２を用いた電池Ｂ２においては、電池Ａ２よりも−１０℃出力比の大幅な向上が確認された。これは化学量論比が３．８の水素吸蔵合金においてはＮｉリッチな反応活性点が増加するためと考えられる。
さらに、ニッケル正極との容量比が１．７で合金の化学量論比が３．９の水素吸蔵合金負極ｃ２を用いた電池Ｃ２においては、合金の化学量論比が増大したことに伴い、電池Ａ２、電池Ｂ２よりも更に−１０℃出力比の向上が確認された。これは化学量論比が３．９の水素吸蔵合金においてはＮｉリッチな反応活性点が顕著に増加するためと考えられる。 Further, in the battery B2 using the hydrogen storage alloy negative electrode b2 having a capacity ratio of 1.7 with respect to the capacity of the nickel positive electrode and a stoichiometric ratio of the alloy of 3.8, the output ratio is significantly larger than that of the battery A2. Improvement was confirmed. This is presumably because Ni-rich reactive sites increase in a hydrogen storage alloy having a stoichiometric ratio of 3.8.
Further, in the battery C2 using the hydrogen storage alloy negative electrode c2 having a capacity ratio with the nickel positive electrode of 1.7 and a stoichiometric ratio of the alloy of 3.9, the stoichiometric ratio of the alloy has increased. It was confirmed that the output ratio was further improved by −10 ° C. than the batteries A2 and B2. This is considered to be because Ni-rich reactive sites increase significantly in a hydrogen storage alloy having a stoichiometric ratio of 3.9.

これらに対して、ニッケル正極の容量との容量比が１．２で合金の化学量論比が３．５の水素吸蔵合金負極ａ１を用いた電池Ａ１においては、電池Ａ２に比較して−１０℃出力比が大幅な低下が確認された。これは、ニッケル正極の容量との容量比が１．２となるようにしたことにより、水素吸蔵合金量が減少して負極全体での反応活性点数が減少し、これに起因して、特に、低温領域で顕著な出力低下が現れたものと考えられる。   On the other hand, in the battery A1 using the hydrogen storage alloy negative electrode a1 having a capacity ratio of 1.2 with respect to the capacity of the nickel positive electrode and a stoichiometric ratio of 3.5 with respect to the alloy, it is −10 compared with the battery A2. A drastic decrease in the output ratio of ℃ was confirmed. This is because the capacity ratio with the capacity of the nickel positive electrode is 1.2, so that the amount of hydrogen storage alloy is reduced and the number of reaction active points in the whole negative electrode is reduced. It is considered that a significant decrease in output appears in the low temperature region.

また、ニッケル正極の容量との容量比が１．２で合金の化学量論比が３．８の水素吸蔵合金負極ｂ１を用いた電池Ｂ１においては、電池Ａ２に比較して−１０℃出力比の向上が確認された。これは、ニッケル正極の容量との容量比が１．２となるようにしたことによる水素吸蔵合金量の減少に伴う反応活性点数の減少と、高化学量論比合金による反応活性点数の増加との影響が現れる。ところが、この場合は、高化学量論比合金による反応活性点数の増加効果が上回って、低温出力の向上が図られたものと考えられる。   In addition, in the battery B1 using the hydrogen storage alloy negative electrode b1 having a capacity ratio of 1.2 with respect to the capacity of the nickel positive electrode and a stoichiometric ratio of the alloy of 3.8, the output ratio is −10 ° C. as compared with the battery A2. Improvement was confirmed. This is because the decrease in the number of reaction active points due to the decrease in the amount of hydrogen storage alloy due to the capacity ratio with the capacity of the nickel positive electrode being 1.2, and the increase in the number of reaction active points due to the high stoichiometric ratio alloy The effect of. However, in this case, it is considered that the increase in the number of reaction active sites by the high stoichiometric alloy exceeds the effect of increasing the low temperature output.

さらに、ニッケル正極の容量との容量比が１．２で合金の化学量論比が３．９の水素吸蔵合金負極ｃ１を用いた電池Ｃ１においては、電池Ｂ１よりも更に−１０℃出力比の向上が確認された。これは水素吸蔵合金の化学量論比が大幅に増大したことに伴い、水素吸蔵合金表面のＮｉリッチな反応活性点数が大幅に増加したことによるものと考えられる。   Furthermore, in the battery C1 using the hydrogen storage alloy negative electrode c1 having a capacity ratio of 1.2 with respect to the capacity of the nickel positive electrode and a stoichiometric ratio of the alloy of 3.9, the output ratio is further −10 ° C. than the battery B1. Improvement was confirmed. This is thought to be due to the fact that the number of Ni-rich reaction active points on the surface of the hydrogen storage alloy has increased significantly as the stoichiometric ratio of the hydrogen storage alloy has increased significantly.

（２）耐久性試験
ついで、これらの各電池Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２の部分充放電サイクル試験と完全充放電サイクル試験とからなる耐久性試験を以下のようにして行った。
ａ．部分充放電サイクル試験
まず、これらの各電池Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２において、１０Ｉｔの充電電流にてＳＯＣ（State Of Charge：充電深度）が８０％となる電圧まで充電した後、１０Ｉｔの放電電流にてＳＯＣが２０％となる電圧まで放電させるという充放電サイクルを繰り返す部分充放電サイクル試験を行った。そして、このような部分充放電サイクルを放電電気量が１０ｋＡｈとなるまで繰り返した。 (2) Durability Test Next, a durability test including a partial charge / discharge cycle test and a full charge / discharge cycle test of each of the batteries A1, B1, C1, A2, B2, C2 was performed as follows.
a. Partial charge / discharge cycle test First, in each of these batteries A1, B1, C1, A2, B2, and C2, after charging to a voltage at which SOC (State Of Charge) is 80% at a charging current of 10 It, A partial charge / discharge cycle test was repeated in which a charge / discharge cycle of discharging to a voltage at which the SOC became 20% was performed at a discharge current of 10 It. Then, such a partial charge / discharge cycle was repeated until the amount of electric discharge became 10 kAh.

ついで、２５℃の雰囲気中で、各電池Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２の部分充放電サイクル試験後の出力を求めた後、電池Ａ２の部分充放電サイクル試験後の出力を１００とし、他の電池Ａ１，Ｂ１，Ｃ１，Ｂ２，Ｃ２の部分充放電サイクル試験後の出力を電池Ａ２との比率（相対値）として求め、これを部分充放電サイクル試験後の耐久性として表すと下記の表２に示すような結果となった。   Next, after obtaining the output after the partial charge / discharge cycle test of each of the batteries A1, B1, C1, A2, B2, and C2 in an atmosphere at 25 ° C., the output after the partial charge / discharge cycle test of the battery A2 is set to 100. The output after the partial charge / discharge cycle test of other batteries A1, B1, C1, B2, and C2 is obtained as a ratio (relative value) to the battery A2, and this is expressed as the durability after the partial charge / discharge cycle test. The results shown in Table 2 were obtained.

ｂ．完全充放電サイクル試験
一方、これらの各電池Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２において、室温（約２５℃）で、それぞれ１Ｉｔの充電々流で充電し、満充電に達した後、電池電圧が１０ｍＶ低下（−ΔＶ＝１０ｍＶ）した時点で充電を１時間休止させた後、１Ｉｔの放電電流で終止電圧が０．９Ｖになるまで放電させるという充放電サイクルを繰り返す完全充放電サイクル試験を行った。そして、このような完全充放電サイクルを放電電気量が１０ｋＡｈとなるまで繰り返した。 b. Full charge / discharge cycle test On the other hand, in each of these batteries A1, B1, C1, A2, B2, and C2, the batteries were charged at a charging current of 1 It at room temperature (about 25 ° C.) and reached the full charge. A complete charge / discharge cycle test in which the charge / discharge cycle is repeated by stopping the charging for 1 hour when the voltage drops by 10 mV (-ΔV = 10 mV) and then discharging until the final voltage becomes 0.9 V with a discharge current of 1 It. went. Then, such a complete charge / discharge cycle was repeated until the amount of discharged electricity reached 10 kAh.

ついで、２５℃の雰囲気中で、各電池Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２の完全充放電サイクル試験後の出力を求めた。この後、先に求めた電池Ａ２の部分充放電サイクル試験後の出力を１００とし、電池Ａ１，Ｂ１，Ｃ１，Ａ２，Ｂ２，Ｃ２の完全充放電サイクル試験後の出力を電池Ａ２の部分充放電サイクル試験後の出力との比率（相対値）として求め、これを完全充放電サイクル試験後の耐久性として表すと下記の表２に示すような結果となった。

Figure 0005241188
Subsequently, the output after the complete charging / discharging cycle test of each battery A1, B1, C1, A2, B2, C2 was calculated | required in 25 degreeC atmosphere. Thereafter, the output after the partial charge / discharge cycle test of the battery A2 obtained above is set to 100, and the output after the full charge / discharge cycle test of the batteries A1, B1, C1, A2, B2, and C2 is set as the partial charge / discharge of the battery A2. When obtained as a ratio (relative value) to the output after the cycle test and expressed as the durability after the complete charge / discharge cycle test, the results shown in Table 2 below were obtained.
Figure 0005241188

上記表２の結果から、以下のことが明らかになった。即ち、ニッケル正極の容量との容量比が１．７で合金の化学量論比が３．５の水素吸蔵合金負極ａ２を用いた電池Ａ２の部分充放電サイクル試験後の出力を１００とした場合、完全充放電サイクルを行うときには、ニッケル正極の容量との容量比が１．７（電池システムＡ２２，Ｂ２２，Ｃ２２）であっても、１．２（電池システムＡ１２，Ｂ１２，Ｃ１２）であっても、あるいは化学量論比が３．５（電池Ａ２，Ａ１）であっても、３．８（電池Ｂ２，Ｂ１）であっても、３．９（電池Ｃ２，Ｃ１）であっても、即ち、電池システムＡ１２，Ｂ１２，Ｃ１２，Ａ２２，Ｂ２２，Ｃ２２のいずれであっても、耐久性が低下することが分かる。これは、完全充放電サイクルを繰り返すことにより水素吸蔵合金の微粉化が進行するためと考えられる。   From the results in Table 2 above, the following became clear. That is, when the output after the partial charge / discharge cycle test of the battery A2 using the hydrogen storage alloy negative electrode a2 having a capacity ratio of 1.7 to the nickel positive electrode and an alloy stoichiometry of 3.5 is 100 When the complete charge / discharge cycle is performed, the capacity ratio with respect to the capacity of the nickel positive electrode is 1.7 (battery systems A22, B22, C22), but 1.2 (battery systems A12, B12, C12) Or the stoichiometric ratio is 3.5 (battery A2, A1), 3.8 (battery B2, B1), 3.9 (battery C2, C1), That is, it can be seen that the durability is lowered in any of the battery systems A12, B12, C12, A22, B22, and C22. This is thought to be because the pulverization of the hydrogen storage alloy proceeds by repeating the complete charge / discharge cycle.

なお、ニッケル正極の容量との容量比が１．２で、化学量論比が３．５の電池Ａ１および化学量論比が３．８の電池Ｂ１ならびに化学量論比が３．９の電池Ｃ１においては、負極全体としての酸素ガス吸収量が減少して内圧上昇による質量減を引き起こし、また負極活物質の芯体から剥れが起こりやすくなるため、サイクル経過時には出力低下により耐久性がさらに低下したものと考えられる。   A battery A1 having a capacity ratio to the capacity of the nickel positive electrode of 1.2, a stoichiometric ratio of 3.5, a battery B1 having a stoichiometric ratio of 3.8, and a battery having a stoichiometric ratio of 3.9 In C1, the oxygen gas absorption amount as a whole of the negative electrode is reduced, causing a decrease in mass due to an increase in internal pressure, and peeling off from the core of the negative electrode active material is likely to occur. It is thought that it decreased.

一方、部分充放電サイクルを行うときには、ニッケル正極の容量との容量比が１．７（電池システムＡ２１，Ｂ２１，Ｃ２１）であれば、化学量論比が３．５（電池Ａ２）であっても、３．８（電池Ｂ２）であっても、３．９（電池Ｃ２）であっても、耐久性は同等となることが分かる。
ところが、部分充放電サイクルを行うときには、ニッケル正極の容量との容量比が１．２（電池システムＡ１１）になると、化学量論比が３．５（電池Ａ１）になると、耐久性はこれらの電池Ａ２，Ｂ２，Ｃ２と同等であるが、−１０℃出力比が低下することが分かる。このことは、化学量論比が３．５の水素吸蔵合金を用いる場合は、水素吸蔵合金の質量を低減させると低温出力特性が低下することを意味している。 On the other hand, when the partial charge / discharge cycle is performed, if the capacity ratio to the capacity of the nickel positive electrode is 1.7 (battery systems A21, B21, C21), the stoichiometric ratio is 3.5 (battery A2). Also, it can be seen that the durability is the same regardless of whether it is 3.8 (battery B2) or 3.9 (battery C2).
However, when performing a partial charge / discharge cycle, when the capacity ratio to the capacity of the nickel positive electrode is 1.2 (battery system A11), the stoichiometric ratio is 3.5 (battery A1), and the durability is Although it is equivalent to batteries A2, B2, and C2, it can be seen that the output ratio of −10 ° C. decreases. This means that when a hydrogen storage alloy having a stoichiometric ratio of 3.5 is used, the low temperature output characteristics are lowered when the mass of the hydrogen storage alloy is reduced.

しかしながら、部分充放電サイクルを行うときには、ニッケル正極の容量との容量比が１．２（電池システムＢ１２，Ｃ１２）になっても、即ち、水素吸蔵合金の質量を低減させても、化学量論比が３．８（電池Ｂ１）であっても、３．９（電池Ｃ１）であっても、耐久性はこれらの電池Ａ２，Ｂ２，Ｃ２と同等であるとともに、−１０℃出力比もそれほど低下しないことが分かる。このことは、部分充放電サイクルを行うときには、ニッケル正極の容量との容量比が１．２になっても、化学量論比が３．８以上の水素吸蔵合金を用いれば、電池としてのコストおよび質量を低減することが可能となることを意味している。   However, when the partial charge / discharge cycle is performed, even if the capacity ratio to the capacity of the nickel positive electrode is 1.2 (battery systems B12, C12), that is, the mass of the hydrogen storage alloy is reduced, Whether the ratio is 3.8 (battery B1) or 3.9 (battery C1), the durability is equivalent to these batteries A2, B2, and C2, and the output ratio of -10 ° C. is not so much. It turns out that it does not fall. This means that when a partial charge / discharge cycle is performed, even if the capacity ratio with respect to the capacity of the nickel positive electrode is 1.2, if a hydrogen storage alloy having a stoichiometric ratio of 3.8 or more is used, the cost of the battery is reduced. It also means that the mass can be reduced.

したがって、電池としてのコストおよび質量を低減することが可能とするためには、水素吸蔵合金負極の負極活物質となる水素吸蔵合金は化学量論比が３．８以上のもの用いるとともに、ニッケル正極の容量との容量比が１．２以下となるように水素吸蔵合金負極を調整し、このような水素吸蔵合金負極を用いてニッケル−水素蓄電池を構成する。
そして、ハイブリッド自動車や電気自動車などのような車輌関係の用途に用いる場合には、このようなニッケル−水素蓄電池の複数個を用いて組電池にするとともに、この組電池が部分充放電サイクルを繰り返して行えるように部分充放電制御が可能な充放電制御手段を設ける必要がある。
この場合、部分充放電制御としては、上述したように充電深度（ＳＯＣ）が２０％相当の電圧に達すると放電を停止して充電を開始し、充電深度（ＳＯＣ）が８０％相当の電圧に達すると充電を停止して放電を開始するようになされるのが好ましい。 Therefore, in order to reduce the cost and mass of the battery, a hydrogen storage alloy serving as the negative electrode active material of the hydrogen storage alloy negative electrode has a stoichiometric ratio of 3.8 or more, and a nickel positive electrode The hydrogen storage alloy negative electrode is adjusted so that the capacity ratio with respect to the capacity of the battery becomes 1.2 or less, and a nickel-hydrogen storage battery is configured using such a hydrogen storage alloy negative electrode.
And when using it for the vehicle-related use like a hybrid vehicle or an electric vehicle, while making an assembled battery using a plurality of such nickel-hydrogen storage batteries, this assembled battery repeats a partial charge / discharge cycle. Therefore, it is necessary to provide charge / discharge control means capable of partial charge / discharge control.
In this case, as the partial charge / discharge control, as described above, when the depth of charge (SOC) reaches a voltage equivalent to 20%, the discharge is stopped and charging is started, and the charge depth (SOC) is set to a voltage equivalent to 80%. When it reaches, it is preferable to stop charging and start discharging.

ここで、水素吸蔵合金は、一般式がＬｎl-xＭｇxＮｉy-a-bＡｌaＭbと表され、０．１≦ｘ≦０．２、３．８≦ｙ≦３．９、０．１≦ａ≦０．３、０≦ｂ≦０．２の条件を満たす必要がある。これは、ｘ＞０．２であるとマグネシウムの偏析が生じ、ａ＞０．３であるとアルミニウムの偏析が生じるようになって、それぞれ耐食性の低下をもたらすようになるからである。また、ｙ＜３．８であったり、ｙ＞３．９であったりすると、Ａ5Ｂ19型構造をそれぞれ構成することが困難となるからである。
Here, the hydrogen storage alloy is represented by a general formula Ln lx Mg x Ni yab Al a M b, and 0.1 ≦ x ≦ 0.2. It is necessary to satisfy the conditions of 8 ≦ y ≦ 3.9, 0.1 ≦ a ≦ 0.3, and 0 ≦ b ≦ 0.2. This is because magnesium is segregated when x> 0.2, and aluminum is segregated when a> 0.3, resulting in a decrease in corrosion resistance. In addition, y <3. If it is 8 or y> 3.9, it is difficult to construct the A 5 B 19 type structure.

上述したように、本発明においては、化学量論比の高い水素吸蔵合金を用いて高出力、特に、低温度領域での高出力を確保し、加えて水素吸蔵合金量の大幅削減を行うことで、車両用途おいて必要な高出力・高耐久性を維持しつつ低コストなアルカリ蓄電池システムの提供が可能になる。換言すると、高出力・高耐久性を維持しながら水素吸蔵合金量の大幅削減を行い、安価なアルカリ蓄電池システムを提供できる。   As described above, in the present invention, the hydrogen storage alloy having a high stoichiometric ratio is used to ensure high output, particularly high output in a low temperature region, and in addition, the amount of hydrogen storage alloy is greatly reduced. Thus, it is possible to provide a low-cost alkaline storage battery system while maintaining the high output and high durability required for vehicle applications. In other words, it is possible to significantly reduce the amount of hydrogen storage alloy while maintaining high output and high durability, and to provide an inexpensive alkaline storage battery system.

本発明のアルカリ蓄電池システムに用いられるアルカリ蓄電池を模式的に示す断面図である。It is sectional drawing which shows typically the alkaline storage battery used for the alkaline storage battery system of this invention.

符号の説明Explanation of symbols

１１…水素吸蔵合金負極、１１ｃ…芯体露出部、１２…ニッケル正極、１２ｃ…芯体露出部、１３…セパレータ、１４…負極集電体、１５…正極集電体、１５ａ…集電リード部、１７…外装缶、１７ａ…環状溝部、１７ｂ…開口端縁、１８…封口体、１８ａ…正極キャップ、１８ｂ…弁板、１８ｃ…スプリング、１９…絶縁ガスケット DESCRIPTION OF SYMBOLS 11 ... Hydrogen storage alloy negative electrode, 11c ... Core body exposed part, 12 ... Nickel positive electrode, 12c ... Core body exposed part, 13 ... Separator, 14 ... Negative electrode collector, 15 ... Positive electrode collector, 15a ... Current collection lead part , 17 ... exterior can, 17a ... annular groove, 17b ... opening edge, 18 ... sealing body, 18a ... positive electrode cap, 18b ... valve plate, 18c ... spring, 19 ... insulating gasket

Claims (4)

ニッケルを含む水素吸蔵合金を負極活物質とする水素吸蔵合金負極と水酸化ニッケルを主正極活物質とするニッケル正極とセパレータとからなる電極群をアルカリ電解液とともに外装缶内に備えたアルカリ蓄電池を有するアルカリ蓄電池システムであって、
前記水素吸蔵合金は少なくともＡ５Ｂ１９型構造の結晶構造を有し、かつ該Ａ５Ｂ１９型構造のＡ成分に対するＢ成分のモル比となる化学量論比（Ｂ／Ａ）が３．８以上であるとともに、部分充放電制御するようになされており、
前記部分充放電制御は、充電深度（ＳＯＣ）が１０％〜９５％相当の電圧範囲でのみ充放電されるように制御されていることを特徴とするアルカリ蓄電池システム。 An alkaline storage battery comprising a hydrogen storage alloy negative electrode using a hydrogen storage alloy containing nickel as a negative electrode active material, an electrode group comprising a nickel positive electrode using nickel hydroxide as a main positive electrode active material and a separator in an outer can together with an alkaline electrolyte An alkaline storage battery system comprising:
The hydrogen storage alloy has a crystal structure of at least A 5 B 19 type structure, and the stoichiometric ratio of the molar ratio of B component to A component in the A 5 B 19 type structure (B / A) is 3. 8 and above, and partial charge / discharge control is performed,
The partial charge / discharge control is controlled so that the charge depth (SOC) is charged / discharged only in a voltage range corresponding to 10% to 95% . 前記水素吸蔵合金は、一般式がＬｎl-xＭｇxＮｉy-a-bＡｌaＭb（式中、ＬｎはＹを含
む希土類元素から選択される少なくとも１種の元素で、ＭはＣｏ，Ｍｎ，Ｚｎから選択される少なくとも１種の元素であり、０．１≦ｘ≦０．２、３．８≦ｙ≦３．９、０．１≦ａ≦０．３、０≦ｂ≦０．２）で表されることを特徴とする請求項１に記載のアルカリ蓄電池システム。 Select the hydrogen storage alloy is represented by the general formula is in Ln lx Mg x Ni yab Al a M b ( wherein, Ln is at least one element selected from rare earth elements including Y, M is Co, Mn, and Zn at least a one element, the table in 0.1 ≦ x ≦ 0.2,3. 8 ≦ y ≦ 3.9,0.1 ≦ a ≦ 0.3,0 ≦ b ≦ 0.2) to be The alkaline storage battery system according to claim 1. 前記ニッケル正極の容量Ｘに対する前記水素吸蔵合金負極の容量Ｙの比率となる容量比Ｚ（＝Ｙ／Ｘ）が１．２以下（１．０＜Ｚ≦１．２）であることを特徴とする請求項１または請求項２に記載のアルカリ蓄電池システム。   The capacity ratio Z (= Y / X), which is the ratio of the capacity Y of the hydrogen storage alloy negative electrode to the capacity X of the nickel positive electrode, is 1.2 or less (1.0 <Z ≦ 1.2). The alkaline storage battery system according to claim 1 or 2. 前記部分充放電制御は、充電深度（ＳＯＣ）が２０％相当の電圧に達すると放電を停止して充電を開始し、充電深度（ＳＯＣ）が８０％相当の電圧に達すると充電を停止して放電を開始するようになされていることを特徴とする請求項１から請求項３のいずれかに記載のアルカリ蓄電池システム。
In the partial charge / discharge control, when the depth of charge (SOC) reaches a voltage equivalent to 20%, the discharge is stopped and charging is started. When the depth of charge (SOC) reaches a voltage equivalent to 80%, the charge is stopped. The alkaline storage battery system according to any one of claims 1 to 3, wherein discharge is started.
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